Two-component ceramic coating for silica insulation

ABSTRACT

Low density, fibrous, rigid, silica insulations are rendered impervious to moisture by application of a ceramic glaze coating comprising a silica barrier layer and an emissivity glaze layer comprising a high silica glass component, an emissivity agent and a borosilicate glass component. The resulting ceramic glaze laminate adhered to the fibrous silica insulation provides a moisture-impervious insulating material which exhibits a high emissivity and is resistant to delamination and spalling at repeated cycles of thermal shock.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to ceramic glaze coatings, and more particularly to ceramic glaze coatings for application to low density, fibrous, rigid silica insulation.

2. Description of the Prior Art

In recent years, rigid, fibrous silica insulations have been developed with densities as low as 9 pounds per cubic foot for possible application as a lightweight reusable surface insulating material. Such insulating materials find application, for example, in space shuttle hardware where low density and very low thermal conductivity are requirements for the insulating material. In that the low density, fibrous, refractory, silica insulations are quite porous and readily absorb moisture, it is necessary to coat the surface of such insulations with a coating which renders them impervious to moisture. Also, to be economical for such uses, the insulating materials must be reusable. That is, the insulation must repeatedly withstand the extreme temperature changes of approximately 2,500°F. which are occasioned by re-entry into the atmosphere from space without delamination or spalling of the insulation.

It is known in the art that silicon-containing substrates can be coated with protective ceramic compositions. See, for example, U.S. Pat. Nos. 3,637,425 and 3,458,345. However, such ceramic compositions are inadequate for use in space shuttle applications because they will not withstand repeated severe thermal cycling in the temperature ranges encountered in such applications without delamination. Moreover, such coatings do not provide the high emissivity levels desirable for such applications.

It is an object of the instant invention to provide a ceramic glaze coating for low density, fibrous, rigid silica insulation which overcomes the aforementioned problems. Moreover, it is an object of the present invention to provide a moisture-impervious ceramic glaze coating for rigid, low density, fibrous silica insulations. Further, it is an object of the instant invention to provide a hard ceramic glaze coating with a high emissivity and a low coefficient of thermal expansion which withstands thermal cycling in the range of -250°F. to 2,500°F.

SUMMARY OF THE INVENTION

It has been found that the aforementioned objects are accomplished by coating low density, fibrous, rigid silica insulations with a ceramic glaze coating comprising a silica barrier coat and an emissivity glaze coat consisting essentially of a high silica glass, an emissivity agent and a borosilicate glass. The ceramic glaze laminate coating formed by sequentially applying and firing the two aforementioned coats provides a moisture-impervious insulation which exhibits a high emissivity and is resistant to delamination and spalling at repeated cycles of thermal shock occasioned by re-entry from space.

BRIEF DESCRIPTION OF THE DRAWING

The attached FIGURE depicts a low density, fibrous, silica insulation adhered to a metallic substrate over which is disposed the two-layered ceramic glaze coating of the instant invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the instant invention, there are provided ceramic glaze coatings and a method for treating low density, rigid, fibrous silica insulating materials, generally adhered to a metallic substrate, to thereby render such insulations non-porous and impervious to moisture. Silica insulations coated in accordance with the instant invention are suitable for use in environments in which the insulation must withstand repeated exposures to alternating high and low temperatures. Although the ceramic glaze coatings of this invention are ideally suited for application over fibrous silica insulation substrates, which in turn are generally adhered to a metallic base, the ceramic coatings are also suitable for rendering impervious to moisture other substrates adhered to other base materials or substrates.

The fibrous, silica insulation to which coatings of this invention are applied generally exhibit a density in the range of about 9 to about 20 pounds per cubic foot and are characterized as fibrous. Such insulations exhibit a low coefficient of thermal expansion, generally in the range of 2.0-5.0 × 10⁻ ⁷ inch/inch/°F. and a low emissivity at temperatures in the range of 2,000°-2,500°F. Being fibrous, such insulations readily absorb moisture and, for this reason, must be coated with a suitable ceramic glaze coating.

The first layer or coat of the ceramic glaze coating of the instant invention is designated a barrier coat. One of the functions served by the barrier coat is to separate the fibrous silica insulation substrate from the other layer of the ceramic glaze coating with which it may be reactive. It may also aid in the control of the weight build-up of the emissivity-glaze coating during application of the slurry. Additionally, the barrier coat must have a coefficient of thermal expansion approximately equal to the rigid, fibrous silica insulation substrate so that it will withstand repeated thermal cycles without delamination. Moreover, it must be dense and relatively non-porous. Finally, it must be compatible with the emissivity glaze coating. Although a great number of silica-type materials having a coefficient of thermal expansion near that of the fibrous silica insulation substrate have been evaluated, most are unacceptable. For example, cordierite (2MgO.2Al₂ O₃.SiO₂) was found to be unacceptable in that it could not withstand temperatures in the vicinity of 2,500°F. A refractory cement of the MgO-clay composition (Norton RM 779) was also unacceptable in that it absorbed the glaze overcoat. Other silicas such as Cab-O-Sil (calcined at 2,000°-2,200°F., 200 mesh) and a silica fiber (calcined at 2,000°F.) were also successful.

The barrier coat of the instant invention is a fused silica fired to a hard surface at a temperature in the range of 1,700°-2,500°F. Firing the silica at a temperature in this range is necessary in order to promote sufficient density and reduce the porosity of the barrier coat. The fused silica generally contains not less than 99.6% silica (SiO₂) and is generally applied in aqueous slip form. The fused silica aqueous slip generally contains from about 80% to about 90% solids and the grain size of the silica particles are such that there is no greater than about 3% retention on a Standard No. 325 sieve.

The barrier coat layer is applied in the form of the slip as above-described to a thickness of from about 4 to about 8 mils. A thickness of about 4 mils is considered minimum in order to assure coverage of the fibrous silica insulation substrate. A thickness in excess of 8 mils is satisfactory; however, there is generally little incentive in employing greater thicknesses other than attaining increased strength with an attendant weight increase. After application, the insulating material substrate containing the barrier coat layer is dried and is then placed in a furnace at a temperature of from about 1,700°F. to about 2,500°F. and preferably from about 2,200°F. to about 2,500°F. and fired for approximately 15 minutes. A longer time is acceptable but generally unnecessary. Thereafter, the specimen is cooled to ambient temperature before proceeding with the application of the second layer of the ceramic glaze coating.

The second layer of the instant ceramic glaze coating is designated the emissivity-glaze layer. Its function is to provide in the ceramic glaze coating a high emissivity level to facilitate radiant heat transfer from the ceramic coating during re-entry and to provide for a high degree of reflection of the radiant energy directed at the surface of the ceramic glaze coated substrate. It also provides a smooth, hard, moisture-impervious surface which is resistent to crazing under repeated cycles of thermal shock. The emissivity-glaze coat layer comprises a high refractory emissivity agent incorporated in a glass composition comprising a high silica glass and a borosilicate glass. It has been found that the combination of a high silica glass and a borosilicate glass in the proper ratios provides a suitable overglaze coat which is smooth, free from cracking and is moisture-tight. The use of a high silica glass component alone as the overglaze coat results in a porous coating, whereas the use of a borosilicate glass component alone as the overglaze coat results in a high gloss coating in which crazing is noticeable under the microscope. Only enough of the borosilicate glass should be employed to obtain the desired continuous vitreous surface in the overglaze coat.

Examples of high refractory emissivity agents suitable in the instant invention include silicon carbide, chrome oxide, cobalt oxide, nickel oxide, nickel-chrome spinel, silicon nitride and calcined mixed oxides of iron, chrome and cobalt (Ferro Black Stain F-3794) and mixtures thereof. Preferred emissivity agents are silicon carbide, Ferro Black Stain F-3794 and mixtures thereof. Especially preferred is silicon carbide which provides an emissivity level in the resulting coating of from about 0.89 to about 0.93 at temperatures to 2,500°F. The other emissivity agents provide slightly lower emissivity levels; however, it may be desirable to combine emissivity agents depending upon the spectral range of interest.

The high silica glasses suitably employed in the emissivity-glaze layer generally contain not less than 94% by weight silica with the remainder of the composition being a fluxing agent. Such high silica glasses are generally employed ground to a fine mesh (e.g., 325 mesh). A typical high silica glass has the following composition: silica (SiO₂), 94-97%; fluxing agent, 3-6%. Especially preferred are high silica glasses wherein boric oxide is employed as the fluxing agent. Exemplary of such a high silica glass is Corning Glass Works No. 7913 having the following composition: SiO₂ -96.5%; B₂ O₃ -3.5%. Boric oxide is the preferred fluxing agent because the resultant glasses exhibit a low coefficient of thermal expansion.

The borosilicate glasses suitably employed in the emissivity-glaze layer are those having the following composition: SiO₂, 70-87%; B₂ O₃, 10-20%; Na₂ O, 2-5%; and Al₂ O₃, 1-5%. A typical borosilicate glass composition is Corning Glass Works No. 7740 having the following composition: SiO₂, 80.4%; B₂ O₃, 13.3%; Na₂ O, 4.3%; Al₂ O₃, 2.0%. Both glasses are generally employed ground to a 325 mesh.

The high silica glass component and the borosilicate glass component are employed in a weight ratio of from about 3:1 to about 19:1, with best results being obtained with ratios of from about 9:1 to about 19:1. The tendency toward crazing increases as the borosilicate glass component concentration increases.

While it is equivalently useful to prepare the emissivity-glaze layer employing a single glass component having the same overall composition as the two glass compositions illustrated, such glass compositions are not generally commercially available. The illustration of the two glass component recipe therefore represents only a preferred mode for the practice of this invention. The number of glass components employed to yield the overall composition in any single layer is not to be considered a limitation of the overall inventive concept. Therefore, it is contemplated that a single glass or a plurality of glasses, as described, having the overall composition above described is within the scope of the instant invention.

The emissivity agent is employed in the emissivity-glaze layer in a weight ratio of glass components (high silica glass and borosilicate glass) to emissivity agent of from about 50:1 to about 4:1 with a weight ratio of from about 19:1 to about 4:1 being preferred.

The emissivity-glaze coat layer, as above-described, is generally applied over the barrier coat in the form of an aqueous slurry, or dispersion, in which an effective amount of a suspension or thickening agent is employed to maintain the solids in suspension. One such suitable suspension agent is methyl cellulose. A great many other suspension agents are suitable, as will be readily apparent to one skilled in the art. What constitutes an effective amount of suspension agent will depend upon the efficacy of the particular suspension agent and can be readily determined. Whenever methyl cellulose (powdered, 4,000 cps) is employed, for example, it is used in a relatively dilute aqueous solution, e.g., 0.5 wt.%, and the aqueous solution is generally employed in an amount such that the solids content of the coating composition is from about 10 wt.% to about 90 wt.% with a solids content of from about 25 wt.% to about 75 wt.% being preferred. The emissivity-glaze coat layer in the form of the slurry or dispersion is applied to the cooled specimen over the barrier coat layer by spraying, painting, or other suitable application device. The slurry should be applied to a thickness of from about 9 to about 12 mils. After drying, the emissivity glaze layer is fired at a temperature of from about 1,700°F. to about 2,500°F., and preferably from about 2,200°F. to about 2,500°F., for a period of approximately 15 minutes. The specimen is thereafter allowed to cool to room temperature.

In the accompanying FIGURE, there is depicted a structural laminate illustrating a substrate or base 10 to which there is adhered a layer of rigid, fibrous silica insulation 12 over which there is adhered the barrier layer 14, the emissivity-glaze layer 16 of the ceramic glaze coating of the instant invention.

The ceramic glaze coating described herein can be applied to all contoured shapes and sharp-edged corners without delamination or cracking problems. Conchoidal chipping will occur when the coating is cut on a band saw, but fully coated panels can be machined to an exact final size by grinding with a diamond or alumina wheel without apparent detriment to the coating. Structural laminates or panels formed in accordance with the instant invention are moisture-impervious and will withstand repeated exposure to cyclical temperature differences of from about -250°F. to about 2,500°F. for extended periods without delamination or spalling.

Illustrative of the foregoing discussion and description and not to be interpreted as a limitation on the scope thereof or on the materials herein employed, the following examples are presented.

EXAMPLE I

In the following Example, there are described the preparations of each of the components of the ceramic coating of the instant invention and a description of the application technique by which they are employed.

The Barrier Coat

A fused silica aqueous slip containing approximately 82% solids was prepared using 99.6% silica (SiO₂) and water. The grain size of the fused silica was such that there was less than 3% retention on a Standard No. 325 sieve. The pH of the aqueous slip was adjusted to a pH of from 5 to 7.

The silica slip was applied to a 3 × 3 × 1 inch tile of fibrous silica having a density of approximately 13 pounds per cubic foot. The dense silica slip was applied by brushing with a soft, lint-free brush to a thickness of from about 4 to about 8 mils. The tile was then dried in an oven for 30 minutes at 250°F. after which it was placed in a furnace and fired at 2,200°F. for 15 minutes. It was then allowed to cool to ambient temperature.

The Emissivity-Glaze Coat

To a plastic bottle were added 380 parts by weight of a high silica glass (Corning Glass Works No. 7913; 96.5% SiO₂, 3.5% B₂ O₃), 20 parts by weight silicon carbide (1,200 grit), 20 parts by weight of a borosilicate glass (Corning Glass Works No. 7740; SiO₂ -80.4%; B₂ O₃ -13.3%; Na₂ O-4.3%; Al₂ O₃ -2.0%) and 350 parts by weight of a 0.5% solution of methyl cellulose in water. These materials were dispersed with an air-driven mechanical mixer to form an aqueous slurry.

The emissivity-glaze coat in the form of the aqueous slurry was applied to the cooled specimen by spraying using a Binks spray gun, Model 18-V fitted with a pressure nozzle. The emissivity coat was sprayed to a thickness of 9 to 12 mils. The coating was allowed to air dry for approximately 10 minutes and was then dried in an oven for 30 minutes at 250°F. Thereafter, the specimen was placed in a furnace and heated to 1,000°-1,400°F. for approximately 20 minutes after which it was fired at a temperature of 2,500°F. for 15 minutes. The specimen was then allowed to cool to ambient temperature.

The test specimen was then subjected to an arc-plasma test wherein the specimen was subjected to alternating high and low temperatures. In the test, the specimen was exposed to a pulse consisting of both radiant and convective heating to simulate the temperatures encountered in a reentry into the atmosphere from a space orbit of approximately 100 nautical miles. The sample was then pre-cooled to approximately -250°F. with liquid nitrogen and then exposed to a peak surface temperature of about 2,340°F. over a 50 minute interval. The sample was exposed to 3.5 hours of such cycling wherein the heat-up time from -250°F. to 2,340°F. was approximately 11 minutes and the cool down time was 16 minutes. For the remaining 23 minutes of the 50 minute cycle, the sample was exposed to the peak temperature of 2,340°F. At the completion of the thermal cycling, the test specimen was then tested for moisture-tightness by placing droplets of water on the coated surface and allowing the specimen to stand for 5 minutes. The surface was then examined by microscope. The test specimen showed no absorption of water and there were no apparent cracks in the coating.

EXAMPLE II

To a tile of fibrous silica coated with a silica barrier coat according to the procedure of Example I was applied an emissivity-glaze coat of the following recipe: 360 parts of high silica glass (Corning Glass Works No. 7913), 40 parts of borosilicate glass (Corning Glass Works No. 7740), and 40 parts of Ferro Black Stain F-3794 (calcined mixed oxides of iron, chrome and cobalt). The overall composition of the coating was as follows: SiO₂ -86.2%; B₂ O₃ -4.1%; Na₂ O-0.4%; Al₂ O₃ -0.2%; CoO--Cr₂ O₃ --Fe₂ O₃ --9.1%.

The above emissivity-glaze composition was applied as a slurry in a 0.5% methyl cellulose solution and dried and fired according to the procedure of Example I. The resulting coated fibrous silica tile was then subjected to 35 cycles of thermal cycling between ambient temperature and 2,340°F. according to the procedure of Example I. The specimen was still moisture-tight after the test and showed no evidence of cracking.

EXAMPLE III

To a tile of fibrous silica coated with a silica barrier coat according to the procedure of Example I was applied an emissivity-glaze coat of the following recipe: 320 parts of high silica glass (Corning Glass Works No. 7913), 80 parts of borosilicate glass (Corning Glass Works No. 7740), 40 parts of Ferro Black Stain F-3794, and 20 parts silicon carbide (1,200 grit).

The above emissivity-glaze composition was applied as a slurry in a 0.5% methyl cellulose solution, dried and thereafter fired according to the procedure of Example I. The resulting coated fibrous silica tile was then subjected to thermal cycling tests between ambient temperature and 2,340°F. according to the procedure of Example I. The specimen was still moisture-tight after 3.5 hours of the thermal cycling tests.

From the foregoing description and Examples of this invention, those of ordinary skill in the art may make many modifications and variations therefrom without departing from the scope of the invention as hereinafter claimed. 

It is claimed that:
 1. An insulating structure for withstanding repeated exposure to cyclical temperature changes of from about -250°F. to about 2,500°F., said structure comprising a substrate having thereon a moisture-impervious ceramic laminate coating which comprises:a. a barrier layer consisting essentially of fused silica, said barrier layer adhered to said substrate; and b. an emissivity-glaze layer consisting essentially of a high silica glass, a borosilicate glass having a composition of from about 70 to about 87 wt.% SiO₂, from about 10 to about 20 wt.% B₂ O₃, from about 2 to about 5 wt.% Na₂ O and from about 1 to about 5 wt.% Al₂ O₃, and an emissivity agent selected from the group of silicon carbide, nickel oxide, chrome oxide, cobalt oxide, nickel-chrome spinel, silicon nitride, calcined mixed oxides of iron, chrome and cobalt, and mixtures thereof with the weight ratio of high silica glass to borosilicate glass being from about 3:1 to about 19:1 and the weight ratio of high silica glass plus borosilicate glass to emissivity agent being from about 50:1 to about 4:1.
 2. The insulating structure of claim 1 wherein said barrier layer is from about 4 to about 8 mils in thickness and said emissivity-glaze layer is from about 9 to about 12 mils in thickness.
 3. The insulating structure of claim 1 wherein the weight ratio of high silica glass to borosilicate glass in said emissivity-glaze layer is from about 10:1 to about 19:1.
 4. The insulating structure of claim 3 wherein the weight ratio of the high silica glass plus borosilicate glass to emissivity agent in said emissivity-glaze layer is from about 19:1 to about 4:1.
 5. The insulating structure of claim 4 wherein the emissivity agent is selected from the group of silicon carbide, calcined mixed oxides of iron, chrome and cobalt and mixtures thereof.
 6. The insulating structure of claim 1 wherein said substrate is a low density, rigid, fibrous silica insulation having a density of from about 9 to about 20 pounds per cubic foot.
 7. A method of rendering impervious to moisture a substrate which comprises sequentially applying to said substrate and firing at a temperature of from about 1,700°F. to about 2,500°F.a. a barrier coating consisting essentially of a fused silica slip having from about 80 to about 90 wt.% solids and b. an emissivity-glaze coating consisting essentially of a high silica glass, a borosilicate glass having a composition of from about 70 to about 87 wt.% SiO₂, from about 10 to about 20 wt.% B₂ O₃, from about 2 to about 5 wt.% Na₂ O, and from about 1 to about 5 wt.% Al₂ O₃ and an emissivity agent selected from the group of silicon carbide, nickel oxide, chrome oxide, cobalt oxide, nickel-chrome spinel, silicon nitride, calcined mixed oxides of iron, chrome and cobalt and mixtures thereof, and an effective amount of a suspension agent in an aqueous slurry containing from about 10 to about 90 wt.% solids, with the weight ratio of high silica glass to borosilicate glass being from about 3:1 to about 19:1 and with the weight ratio of high silica glass plus borosilicate glass to emissivity agent being from about 50:1 to about 4:1.
 8. The method of claim 7 wherein the weight ratio of high silica glass to borosilicate glass in the emissivity-glaze coating is from about 10:1 to about 19:1.
 9. The method of claim 8 wherein the weight ratio of high silica glass plus borosilicate glass to emissivity agent in the emissivity-glaze coating is from about 19:1 to about 4:1.
 10. The method of claim 9 wherein the emissivity agent is selected from the group of silicon carbide, calcined mixed oxides of iron, chrome and cobalt and mixtures thereof.
 11. The method of claim 10 wherein the solids content of the emissivity-glaze coating is from about 25 to about 75 wt.%.
 12. The method of claim 11 wherein the suspension agent in the emissivity-glaze coating is methyl cellulose.
 13. The method of claim 7 wherein the substrate is a low density, rigid, fibrous silica insulation having a density of from about 9 to about 20 pounds per cubic foot. 